Metalliferous azo-dyestuffs and process of making same



Patented Feb. 21, 1933 1,898,911

UNETED STATES PATENT @FFEQE FRITZ STRAUB AND WILLI WIDMER, F BASEL,SWITZERLAND, A SSIGNORS TO THE FIRM SOCIETY OF CHEMICAL INDUSTRY INBASLE, 0F BASEL, SVJITZER-LANID METALLIFEROUS AZO-DYES'IUFFS AND PROCESSOF MAKING SAME No .Tirawing. Application filed. November 30, 1931,Serial No. 578,202, and in Switzerland December 16, 1930.

The present invention relates to the manusubstances containing in thenucleus halogen, facture of new metalliferous azo-dyestuffs 'NO SO H orO-alkyl.

It comprises the process of making these dye- Ther.e' may however alsobe used dihystuifs, as Well as the new dyestuffs themdroxyquinolines ord1 (2zt-dihydroxyquino- 5 lve lines) of more complicated constitution,the 55 According to the present invention new latter being capable ofcoupling twice. Such dyestuffs can be obtained by coupling adiazodlhydroxyquinolines may be obtained for excompound of the generalformula ample from the ortho-aminocarboxylic acids or the esters thereofwhich derive from bensonr zidines, aminobenzlmidazoles, amlnoazoso Ibenzenes, aminobenzothlazoles, amlnostll- 803E 0H benes,aminoarylethers, aminocarbazoles, am-

wherein R stands for a phenyl or naphthyl inodiarylmethanes, orsubstitution products radicle, and the hydroxy group directly at of anyof these compounds.

tached to R stands in ortho-position to the The dyestuffs obtainable inaccordance o5 aZo-group, with a coupling component of the with thisinvention dye vegetable and animal general formula fibers variousshades; by after-treatment of on the dyeings with agents which yieldmetal, for eXaInple a chromium or copper compound, their shades may bealtered and their properties of fastness improved. I e I l Particularlyvaluable products are obtained by treating the dyestuffs of this inven-N tion of the general formula 25 in on wherein R stands for hydrogen,alkyl, aralkyl or aryl, and the carbon atoms numbered 5 //4 \5C and 6belong to a phenyl' or naphthyl resl- /6 due. 0: 2 s 30 As diazocomponents there may be used the g/ 80 diazotized orthohydroxyaminodisulfonic acids of the benzene or naphthalene series, fexample di fi d 2 i 1 h 1 wherein R stands for a phenyl or naphthyl4:6-disulfonic acid, l-amino-Q-phenol-kfiradlcleg the Y Q Y grout)attached to R disulfonic acid, 2-amino-l-hydroxynaphtha- Standsthoposltlon to 19116 g p, 1 lens-4: S-disulfonic acid, and 2-amino-l-hy-Stands for y Ogen, yb amlkyl Y droXynaphthalene-3: S-disul-fonic acid.and the carbon atoms mbered 5 and 6 be- The coupling components may bederived 9 83 to P 5 e ph y resldue, 11 Subfrom the most varied primaryand secondary sb'ance Wlth agents yleldmg metal Whlch are '49 aromaticmono-amines. Simple coupling Capable of tormlng Complex metal 00111-components, such as for example 2:4-dihy- P Q h dyfistufis Contammg g pd i li p th p p th p 1 b which combme with mordants; such agents zyl-,1-phenylor l-naphthyl-2:t-dihydroxyyleldmg meml W for pl the 00111- Iquinoline, and 5:6-, 6:7- and 7:8- benzo- Pounds of Chromlum: PP G E b2:et-dihydroxyquinolines may be made, for nickel, manganese, zmc,vanadium and titaexample, from anthranilic acid, N-methyle, nium. Thereare thus obtained metallifer- N-ethyl-, N-benzyl-, N-phenyL,N-naphthyous dyestuffs which may contain only one lanthranilic acid orthe esters thereof, naphmetal, or may contain several metals; in thethylamines or 2-naphthylamine-3-carboxylicmanufacture of dyestuffscontaining several acid, or substitution products ofany of these metals,the several agents yielding metal may be caused to react with thedyestu'if simultaneously or in succession.

The dyestuffs may be treated with the agents yielding metal in an acid,neutral or alkaline medium, with or without suitable additions, and inan open vessel or under pressure; the treatment may occur in the courseof the manufacture of the parent dyestuff or in the dye-bath.

The complex metal compounds obtainable in accordance with the inventionare very readily soluble in water; the may be applied for dyeing orcoloring materials of any kind, such as wool, loaded or unloaded silk,cotton, leather, artificial silks of regenerated cellulose, celluloseesters and cellulose ethers, and 'arnishes having abasis of cellulose, aneutral resin or an artificial resin; they are also useful as pigmentdyestuffs. They dye material yellowish-red, red to violet, very weequalized pure shades; the dyeings are very fast towards water, washing,alkali, fulling and light.

The followingexamples illustrate the invention, the parts being byweight Example 1 on on Alia, n

S 0311 Th is precipitated by means of common salt and separated byfiltration. When dry, it is a dark brown red powder which dissolves inwater to a blue red solution, in caustic soda solution of 10 per cent.strength to an orange solution, in aqueous sodium carbonate solution of10 per cent. strength to an orangered solution, and in cencentratedsulfuric acid to an orange-yellow solution. The dyestufl dyes wool in anacetic acid bath yellow brown shades, by after chroming the dyeings onthe fiber a yellowish red shade is obtained.

nois- E wample 2.

480 parts of the azo-dyestufi made as described in Example parts ofwater and there is added a solution of chromium sulfate made from 88parts of chromium oxide, 17 0 parts of concentrated cent. strength to an11 allowed to run into a mixture,

fastness to 1 are stirred with 7500 sulfuric acid and 600 arts of water.The mixture is heated to boiling for 18-20 hours in a reflux apparatusand the chromium compound of the dyestuff is then precipitated by theaddition of common salt. The dried dyestufi is a red brown owder whichdissolves in water to a red so ution, in a solution of caustic soda orsodium carbonate of 10 per orange-red solution and in concentratedsulfuric acid to an orange yellow solution. The dyestuil dyes wool in asulfuric acid bath very even bright yellowish red shades of goodfast-ness to light and fullmg.

E'mample 3 313 parts of the sodium salt of 2-amin0-1- phenol-4:G-disulfonic acid are diazotized in the usual manner and thediazo-solution is cooled by means of ice to 10 C. of 1000 partsof'water, 220 parts of 7 8-benzo2 4-dihydroxyquinoline, 45 parts ofcaustic soda and 120 parts of calcined sodium carbonate, whilststirring. When coupling is completed, the dyestuif of the formula ([31!OH H035 ran- L l is completely precipitated and seperated by filtration.When dry, it is a dark brown red powder which dissolves in water to ablue red solution, in a solution of caustic soda or sodium carbonate of10 per cent. strength to an orange solution, and in concentratedsulfuric acid to a brown orange solution. The dyestufl (1 es wool in anacetic acid bath brown sha es; bluish red shades are obtained byafter-chroming the d eings.

By treating the azo-d yestufls obtained as described in this example,with chromium sulfate in the manner described in Example 2, there isobtained a dyestufi, which when dry is a brown red powder which is veryreadily soluble in water, in a solution of causticsoda or sodiumcarbonate of 10 per cent. strengthto a red solution, and in concentratedsulfuric acid to an orange yellow solution. In a sulfuric acid bath thedyestuif is very well absorbed by wool, which it dyes very uniformbluish red shades of good falling and light.

Ewample 1,

269 parts of .Z-amino-l-phenol-d:6-disulfonic acid are diazotized in themanner described in Example 1 and coupled in an alkalinemediumwith 220parts of 6:7-benzoof formic acid and 600 parts of water.

2 d-dihydroxyquinoline. The dyestufi' of the formula pH on HO3S- N=N OsHis precipitated by common salt, separated by filtration and dried.

560 parts of this azo-dyestuff are stirred with 7000 parts of water andthere is added a solution of chromium formate made from parts ofchromium hydroxide, 160 parts The mixture is heated to boiling for about20 hours in a reflux apparatus and the chromium compound of the dyestufiis then precipitated by the addition of common salt. lVhen dried, it isa brown red powder which dissolves in a solution of caustic soda orsodium carbonate of 10 per cent. strength to a red solution and inconcentrated sulfuric acid to a blue red solution. The dyestuff dyeswool evenly in a sulfuric acid bath bordeaux red shades of good fastnessto fulling and light.

Example 5 313 parts of the sodium salt of 2-amino-lphenol-4:tS-disulfonic acid are diazotized in the usual manner and thediazo-solution is allowed to run into a mixture, cooled by means of iceto about 10 C., of 900 parts of water, 245 parts of N-phenyl-2-ketol-hydroxy'quinoline, 42 parts of caustic soda and 110parts of calcined sodium carbonate, whilst stirring. When coupling iscomplete, the dyestuff of the formula is precipitated by the addition ofabout 300 parts of common salt and separated by filtration. Wl en driedit is a red brown powder which dissolves in water to a blue redsolution, in a solution of caustic soda of 10 per cent. strength to anorange yellow solution, in a solution of sodium carbonate of 10 percent. strength to an orange red solution, and in concentrated sulfuricacid to a yellow orange solution. The dyestuff dyes wool in an aceticacid bath yellow brown shades; yel

by after- Ewample 6 573 parts of the azo-dyestuff made as de scribed inExample 5 are heated to boiling for about 18 hours together with about6500 parts of water and a solution of chromium sulfate prepared from 70parts of chromium hydroxide, 150 parts of sulfuric acid and 600 parts ofWater. The solution is thereafter neutralized by the addition of causticsoda solution, filtered and concentrated by evaporation. The chromiumcompound thus obtained is a red brown powder which dissolves in water toa red solution, in a solution of caustic soda or sodium carbonate of- 10per cent. strength to an orange solution, and in concentrated sulfuricacid to an orange yellow solution. The dyestuff dyes wool in a sulfuricacid bath uniform yellowish red shades having good properties offastness.

Ezcample 7 161 parts of 2:4-dihydroxyquinoline are suspended in 1300parts of water, while stir ring, adding then 120 parts of caustic soda.To this suspension 330 parts of diazotized 2 amino 1 -hydroxynaphthaleneA 8 disulfonic acid are added, and the whole is stirred for about 40hours at 3035 C. After this time the dyestuff of the formula which hasformed is filtered ofi, and washed with a common salt solution of 10 percent.

, strength.

The dyestuff paste thus obtained is stirred with 5000 parts of water andmixed with a solution of chromium fluoride prepared from 70 parts ofchromium hydroxide, 56 parts of hydrofluoric acid and 600 parts ofwater. The mixture is heated to the boil for 20 hours in a refluxapparatus and the chromium compound of the dyestulf is then separated bymeans of common salt. The dried dyestuff is a dark violet-brown powderwhich dissolves in water to a violet solution, in a solution of causticsoda or sodium carbonate of 10 per cent. strength to a violet redsolution, and in concentrated sulfuric acid to a red solution. Thedyestuff dyes wool in a sulfuricacid bath very level violet tints havinggood properties of fastness.

Ewample 8 190 parts of N -ethyl-2-keto-4-hydroxyqumoline are dissolvedin 1000 parts of concentrated ammonia, and mixed with 330 parts ofdiazotized 2-amino-l-hydroxynaphthalene i: 8-disnlfonic acid. stirredfor 24 hours at -25 the dyestuif of the formula SOaH (S111:

is separated from the filtrate by the addition of common salt.

The resulting dyestufi paste is stirred into 4500 parts of water, andmixed with a solution of chromium fluoride containing parts of chromiumhydroxide. The mixture is heated to the boil for 20 hours in a refluxapparatus. After this time the difliculty soluble impurities areseparated by filtration, and the chromium compound is precipitated fromthe filtrate by the addition of common salt. The dried dyestufi is ared-brown powder which dissolves in water to a violet solution, in asolution of caustic soda of 10 per cent. strength to a red solution, ina solution of sodium carbonate of 10 per cent. strength to a red-violetsolution, and in concentrated sulfuric acid to a red solution. Thedyestufi dyes wool in a sulfuric acid bath level violet tints havinggood properties of fastness.

We claim:

1. In the manufacture of metalliferous azo-dyestufis, the step whichcomprises cou- The whole is C., filtered, and

pling a diazo-compound of the general formula i .-N=;- I-0H sous onwherein R stands for a phenyl or naphthyl radicle, and the hydroxy groupdirectly attached to R stands in ortho-position to the azo-group, with acoupling component of the general formula azo-dyestufis,

general pling a diazo-compound of the formula som Y R-N=N-0H 45 son awherein It stands for hydrogen, alkyl, benzyl or aryl radicles of thebenzene an naphthalene series, and the carbon atoms numbered 5 and 6naphthyl residue.

3. In the manufacture of chromiferous azodyestuffs, the step whichcomprises coupling a diam-compound of the general formula son! -R-N=N0H/-I soil! 011 wherein R stands for a phenylradicle, and the hydroxygroup directly attached to R stands in ortho-position to the azo-group,with a coupling component of the general formula 'fli wherein R standsfor hydrogen, alkyl, benzyl or ary-l radicles of the benzene andnaphthalene series. and the carbon atoms numbered 5 and 6 belong to aphenyl or naphthyl residue.

4. In the manufacture of chromiferous azodyestuffs, the step whichcomprises coupling the diazo-compound of the formula with a couplingcomponent of the general formula wherein R, stands for hydrogen, alkyl,benbelong to a phenyl or stuffs of the general formula zyl or arylradicles of the benzene and naphthalene series, and the carbon atomsnumbered 5 and 6 belong to a phenyl or naphthyl residue.

5. In the manufacture of the chromiferous azo-dyestufi, the step whichcomprises coupling the diazo-compound of the formula V with the couplingcomponent of the formula 3 av \f k N 6. In the manufacture ofmetalliferous azodyestufis, the step which comprises treating with anagent yielding metal capable of form ing lakes with the lake-forminggroup of the azo-dyestufl, azo-clyestuffs of the general formula on ('1SOsH l ama; a 803K OH 7 I I wherein R stands for a phenyl or naphthylradicle, the hydroxy group attached to R stands in ortho-position to theazo -group, R stands for hydrogen, alkyl, henzyl or aryl radiclesof thebenzene and naphthalene serice, and the carbon atoms numbered 5 and 6belong to a phenyl or naphthyl residue.

7. In the manufacture of chromiferous azodyestufis, the step whichcomprises treating with an agent yielding chromium, azo-dyewherein Rstands for a phenyl or naphthyl radicle, the hydroxy group attached to Rstands in ortho-position to the azogroup, R stands for hydrogen, alkyl,benzyl or aryl radicles of the benzene and naphthalene series, and thecarbon atoms numbered 5 and 6 belong to a phenyl or naphthyl residue.

8. In the manufacture of chromiferous aZo-dyestuifs, the step whichcomprises treating with an agent yielding chromium, azo dyestufis of thegeneral formula.

SOsH

wherein R stands for hydrogen, alkyl, ben- Zyl or aryl radiclcs of thevbenzene and naphthalene series, and the carbon atoms numbered 5 and 6belong to a phenyl or naphthyl residue. 7

10. In the manufacture of the chromiferous azo-dyestuif, the step whichcomprises treating with an agent'yielding chromium, the azo-dyestufl' ofthe formula )3 on Ho3s N=N- T O: N SOsH 11. Process for the manufactureof a metalliferous azo-dyestufis, consisting in coupling adiazo-compound of the general formula SOaH RN=NOH 80311 OH wherein Rstands for a phenyl or naphthyl radicle, and the hydroxy group directlyattached to R stands in ortho-position to the azo-group, with a couplingcomponent of the general formula OH t 4 o5 3 wherein R stands forhydrogen, zyl or aryl radicles of the benzene and naphthalene series,and the carbon atoms numbered 5 and 6 belong to a phenyl or naphthylresidue, and then treating the azo-dyestufls thus obtained of thegeneral formula on C som V 4X RN=NG3 5 50:11 3

l N l R:

wherein R stands for a phenyl or naphthyl radicle, and the hydroxy groupdirectly attached to R stands in ortho-position to the azo-group, with acoupling component of the general formula on t s 5 a --K II o -ce 0wherein R stands for hydrogen, alkyl. benzyl or aryl radicles of thebenzene and naphthalene series, and the carbon atoms numbered 5 and 6belong to a-phenyl or naphthyl residue, and then treating theamdyestufls thus obtained of the general formula in HzN-G SOr AH 1 N lR1 wherein R stands for a phenyl or naphthyl radicle, the hydroxy groupattached to R stands in ortho-position to the azo-group, R stands forhydrogen, alkyl, benzyl or aryl radicles of the benzene and naphthaleneseries, and the carbon atoms numbered 5 alkyl, benand 6 belong to aphenyl or naphthyl residue, an agent yielding chromium.

13. Process for the manufacture of chromiferous azo-dyestufis,consisting in coupling a diazo-compound of the general formula sod!R-N=N-OH son 5 wherein R stands for a phenyl radicle, and

the hydroxy group directly attached to R stands in ortho-position to theazo-group,

with a coupling component of the general formula.

(1)}! /Z\ 5 ao-a wherein R stands for hydrogen, alkyl. benzyl or arylradicles of the benzene and naphthalene series, and the carbon atomsnumbered 5 and 6 belong to a phenyl or naphthyl residue, and thentreating the amdyestuffs thus obtained of the general formula i whereinR stands for a phenyl radicle, the hydroxy group attached to R stands inortho-position to the azo-group, R stands for hydrogen, alkyl, benzyl oraryl radicles of the and naphthalene series, and the carbon atomsnumbered 5 and 6 belong to a phenyl or naphthyl residue, with an agentyielding chromium.

14. Process for the manufacture of chromiferous azo-dyestufis,consisting in coupling the diazo-compound of the formula with a couplingcomponent of the general formula OR a 5 30-11 wherein R stands forhydrogen, alkyl, benzyl or aryl radicles of the benzene and naphthaleneseries, and the carbon atoms numbered 5 and 6 belong to a phenyl ornaphthyl residue, and then treating the amdyestuffs thus obtained of thegeneral formula SOaH with the coupling component of the formula and thentreating the azo-dyestufi' thus obtained of the formula on on H03sN=NI/\ O N S OSH E l with an agent yielding chromium.

16. As new products the metal compounds of azo-dyestulfs of the generalformula wherein R stands for a phenyl or naphthyl radicle, the hydroxy'group attached to R stands in ortho-position to the azo-group, R standsfor hydrogen, alkyl, benzyl or aryl radicles of the benzene andnaphthalene series, and the carbon atoms numbered 5 and 6 belong to aphenyl or naphthyl residue,

which products are orange to red-brown to red to violet colored powderswhich are very easily solublein water, and dye vegetable and animalfibers yellowish-red to red to violet tints.

17. As newproducts the chromuim compounds of azo-dyestufis of thegeneral forwherein R stands for a phenyl or naphthyl radicle, thehydroxy group attached to R stands in .ortho-positoin to the azo-group,R stands for hydrogen, alkyl, benzyl or aryl radicles of the benzene andnaphthalene series, and the carbon atoms numbered 5 and belong to aphenyl or naphthyl residue, which products are orange to red-brown tored to violet colored powders which are very easily soluble in water,and dye vegetable and animal fibers yellowish-red to red to violettints.

18. As new products the chromium compoulnds of azo-dyestuiis of thegeneral formu a SOzH BOJH A N it wherein R stands for a phenyl radicle,the hydroxy group attached to R stands in orthoposition to theazo-group, R stands for hydrogen, alkyl, benzyl or aryl radicles of thebenzene and naphthalene series, and the carbon atoms numbered 5 and 6belong to a phenyl or naphthyl residue, which products are orange tored-brown to red colored powders which are very easily soluble in water,and dye vegetable and animal fibers yellowish-red to red tints.

19. As new products the chromium compounds of azo-dyestufl's of thegeneral formula wherein R stands for hydrogen, alkyl, benzyl or arylradicles of the benzene and naphthalene series, and the carbon atomsnum- 1cm zoo bered and 6 belong to a phenyl or naphthyl residue, whichproducts are orange to redbrown to red colored powders which are veryeasily soluble in water, and dye vegetable 5 and animal fibersyellowish-red to red tints. 20. As a new. product the chromium compoundof the azo-dyestufi of the formula OH OH 1T OuH H which product is ared-brown powder which is very easily soluble in water, and dyesvegetable and animal fibers yellowish-red tints.

In witness whereof we have hereunto signed our names this th day ofNovember, 1931. 20 FRITZ STRAUB. WILLI WIDMER.

